WO2004052897A1

WO2004052897A1 - Phosphorus-containing organosilicon compounds, process for production thereof, and resin compositions or coating compositions containing the same

Info

Publication number: WO2004052897A1
Application number: PCT/JP2003/015676
Authority: WO
Inventors: Hiroaki Shoji
Original assignee: Nippon Unicar Company Limited
Priority date: 2002-12-10
Filing date: 2003-12-08
Publication date: 2004-06-24
Also published as: JP4553734B2; US7223880B2; AU2003289297A1; DE10392233T5; US20050154223A1; JPWO2004052897A1

Abstract

The invention relates to novel phosphorus-containing organosilicon compounds to which the performances of an oxaphosphorin compound are imparted; a process for the production of the compounds; and resin compositions (such as polyester or polycarbonate resin compositions or coating compositions) which contain the compounds. The invention provides phosphorus -containing organosilicon compounds characterized by having in the molecule a phosphorus-containing group (X group) of the general formula (1) which is bonded to the silicon atom; a process for the production of the compounds; and resin compositions or coating compositions which contain the compounds.

Description

Phosphorus-containing organic silicon compound, method for producing the same, resin composition containing the same, or coating composition

The present invention relates to a novel phosphorus-containing organic silicone compound, a method for producing the same, and a resin composition or coating composition containing the same, and more specifically, it has a phosphorus-containing group bonded to a silicon atom in the molecule. The present invention relates to a phosphorus-containing organic silicon compound to which the performance of an oxaphosphorin compound is imparted, a method for producing the same, and a resin composition or a coating composition containing the same. Background art

Oxaphosphoryl compounds are useful as flame retardant additives for resins, and phosphorus-containing dicarboxylic acids derived therefrom are useful as polymer plasticizers. For example, when a phosphorus-containing dicarboxylic acid is used as a comonomer in the production of polyester, a flame retardant polyester can be obtained, and thus, in the production of a resin composition having a flame retardant action, it is derived from oxaphosphorine compound. Phosphorus-containing dicarboxylic acids can be suitably used.

In addition, phosphorus-containing dicarboxylic acids and their ester derivatives have flame resistance, flame retardancy, antibacterial properties (especially antibacterial durability), and are also considered safe. It is also known that it is a component of a polyester composition capable of forming a molded article such as a film or the like (for example, JP-A-2000-021245). See).

In addition, various silicon compounds can strengthen the bond between inorganic materials such as metals and inorganic fillers and organic resins (coupling function), coat the surface of inorganic materials and organic materials, and blend or copolymerize with resins. It is widely used as its surface performance and resin modifier (eg, water repellency, mold release performance, lubrication performance, heat resistance, flexibility, impact resistance, etc.).

Furthermore, it is known that phosphorylated polyorganosiloxane also has a flame retardant effect and has a performance as a flame retardant (for example, JP-A-20001-246582). (Refer to the claims etc.)).

However, stable binding of oxaphosphorine compounds and cinnamate compounds, which have both good and excellent performance, has not been proposed until now.

Therefore, there has been a demand for a silicon compound to which the performance of oxaphosphorin compound can be applied industrially. In addition, there has been a demand for a resin composition having improved performance and a coating composition by blending it.

The object of the present invention is to provide a novel phosphorus-containing organic silicon compound to which the performance of oxaphosphorin compound has been imparted, a method for producing the same and a resin composition containing the same, in particular a polyester resin or polycarbonate resin composition, It may provide a coating composition. Disclosure of the invention

As a result of earnest studies to solve the above-mentioned problems, the present inventors have found that 3,4,5,6-dibenzodi-1,2-oxaphosphate ani-2-oxide (alias: 9) as an oxaphosphorin compound. , 10 0-Dihydro 1 9-Oxer 1 0-Hosphaphenanthrene 1 1 0 0-Oxide), and this is reacted with a silicon compound having an unsaturated ester group to obtain oxaphosphorin. It has been found that a novel phosphorus-containing organic key compound is obtained which is given the performance of the compound. The present invention has been completed on the basis of these findings and further studies.

That is, according to the first aspect of the present invention, a phosphorus-containing group is characterized in that it has a phosphorus-containing group (X group) represented by the following general formula (1) bonded to a carbon atom in the molecule. An organosilicon compound is provided.

General formula (1): 广-R ¹ 0 0

; \ II II

! ^{^{PR 3 -C OR 4 - (1}} )

R ² (0) m

(Wherein, R ¹ and R ² are the same or different and each is a linear or branched alkyl group having 1 to 8 carbon atoms, and an alicyclic group having 5 to 6 carbon atoms in the ring , Unsubstituted youth having 6 to 10 carbon atoms. Or a substituted aryl group or one forming a 5- to 8-membered ring with a phosphorus atom, m is 0 or 1, and R ³ and R ⁴ are each independently substituted or unsubstituted It shows a divalent hydrocarbon group. )

Further, according to the second invention of the present invention, the following general formula (2):

X. R ⁵ HS i O (4-a-b) 2

[Wherein, x is a general formula (1): rR ¹ 0 0

^{^{PR 3 -C 0- R 4 - (}} 1)

^L R ² (0) m

(Wherein, R ¹ and R ² are the same or different and each is a linear or branched alkyl group having 1 to 8 carbon atoms, and an alicyclic group having 5 to 6 carbon atoms in the ring , An unsubstituted or substituted aryl group having 6 to 10 carbon atoms, or one forming a 5- to 8-membered ring with a phosphorus atom, m is 0 or 1; R ³ and R ⁴ each independently represent a substituted or unsubstituted divalent hydrocarbon group)), and R ⁵ represents an alkyl group having 1 to 30 carbon atoms, And the same or different organic group selected from aryl group, alkaryl group, fluorine-substituted alkyl group or alkoxy group; ≤ b ≤ indicates the number in the range of 3.0. A phosphorus-containing organic silicon compound is provided, which is characterized in that

Furthermore, according to a third aspect of the present invention, there is provided a phosphorus-containing organic silicon compound characterized in that, in the second aspect, the general formula (2) is represented by the following general formula (3) Ru.

General formula (3):

R% S i O- (R ⁵ ₂ S i)) x (R ⁵ X S i)) y S i R (3)

(Wherein, R ⁵ and X represent the same as above, X is an integer of 0 or 1 or more, and y is an integer of 1 or more)

According to the fourth aspect of the present invention, the following general formula (4):

X S i R (OR (3-c) 4

[Wherein, X is a general formula (1): rR ¹ 0 0

PR ³ -C o- ⁴ (1)

-R ² (0) m

(Wherein, R ¹ and R ² are the same or different and each is a linear or branched alkyl group having 1 to 8 carbon atoms, and an alicyclic group having 5 to 6 carbon atoms in the ring , Unsubstituted or having 6 to 10 carbon atoms Or a substituted aryl group or one forming a 5- to 8-membered ring together with a lin atom, m is 0 or 1, and R ³ and R ⁴ are each independently substituted Or an unsubstituted divalent hydrocarbon group. R ⁶ is a phosphorus-containing group represented by the formula: R ⁶ represents the same or different organic group selected from an alkyl group having 1 to 30 carbon atoms, a aryl group, an aryl group and a fluorine-substituted alkyl group; ⁷ is the same or different organic group selected from an alkyl group having 1 to 30 carbon atoms, a aryl group, an aryl group or a fluorine-substituted alkyl group, and c is 0 or 1. There is provided a phosphorus-containing organic key compound or a condensate thereof, which is characterized in that

According to the fifth invention of the present invention, the following general formula (5):

XS i R ⁵ . (OS i R 3 (3-c) 5

[Wherein, x is a general formula (1) -E ¹ 0 0

P — R ³ — C 0 1 (1) R ² (o) m

(Wherein, R ¹ and R ² are the same or different and each is a linear or branched alkyl group having 1 to 8 carbon atoms, and an alicyclic group having 5 to 6 carbon atoms in the ring , Form a 5- to 8-membered ring together with an unsubstituted or substituted aryl group having 6 to 10 carbon atoms, or a phosphorus atom M is 0 or 1, and R ³ and R ⁴ each independently represent a substituted or unsubstituted divalent hydrocarbon group. And R ⁵ represents a homogeneous or heterogeneous organic group selected from an alkyl group having 1 to 30 carbon atoms, a aryl group, an aryl group, a fluorine-substituted alkyl group or an alkoxy group. R ⁸ represents an alkyl group having 1 to 30 carbon atoms, an aryl group, an aryl group, an arylalkyl group, a fluorine-substituted alkyl group, or an organic group of the same or different type selected from alkoxy groups; is there. There is provided a phosphorus-containing organic silicon compound characterized by being represented by the formula:

According to the sixth invention of the present invention, in any of the first to fifth inventions, the phosphorus-containing group (X group) is represented by the following general formula (6):

(Wherein, R ³ and R ⁴ each independently represent a substituted or unsubstituted divalent hydrocarbon group) or a phosphorus-containing organic silicon compound or a compound represented by the formula The condensate is provided.

On the other hand, according to the seventh invention of the present invention, the following general formula (7): PH (7 to R ² (0) m

(Wherein, R ¹ and R ² are the same or different and each is a linear or branched alkyl group having 1 to 8 carbon atoms, and an alicyclic group having 5 to 6 carbon atoms in the ring And an unsubstituted or substituted aryl group having 6 to 10 carbon atoms, or one forming a 5- to 8-membered ring with a phosphorus atom, and m is 0 or 1. And a compound represented by the following general formula (8) bonded to a silicon atom in the molecule:

0

R ⁹ -C OR ^ 8

(Wherein, R ⁴ represents a substituted or unsubstituted divalent hydrocarbon group, and R ⁹ represents a substituted or unsubstituted unsaturated hydrocarbon group). It has an unsaturated ester group represented by The method for producing the phosphorus-containing organic silicon compound or the condensate thereof according to any one of the first to sixth inventions, which is obtained by reacting with a silicon compound is provided.

According to the eighth invention of the present invention, the following general formula (7) PH (7)

^L R ² (0) m

(Wherein, R ¹ and R ² are the same or different and each is a linear or branched alkyl group having 1 to 8 carbon atoms, and an alicyclic group having 5 to 6 carbon atoms in the ring And an unsubstituted or substituted aryl group having 6 to 10 carbon atoms, or one forming a 5- to 8-membered ring with a phosphorus atom, and m is 0 or 1. And a compound represented by the following general formula (9):

YS i R ⁶ _C (OR ⁷ ) (3-c) 9

[Wherein, Y is a general formula (8):

0

^{^{R 9 - C 0-R 4}} - 8

(Wherein, R ⁴ represents a substituted or unsubstituted divalent hydrocarbon group, and R ⁹ represents a substituted or unsubstituted unsaturated hydrocarbon group), which is an unsaturated ester group represented by And R ^{6 each} represent an alkyl group having 1 to 30 carbon atoms, a aryl group, R ⁷ represents a same or different organic group selected from an alkyl group or a fluorine-substituted alkyl group, and R ⁷ represents a same or a group selected from an alkyl group having 1 to 30 carbon atoms, a aryl group, an aryl group or a fluorine-substituted alkyl group Indicates a different organic group, c is 0 or 1. ] The method for producing a phosphorus-containing organic silicon compound according to the fourth invention, or a condensate thereof, which is obtained by the reaction with a silicon compound represented by the above.

Further, according to the ninth invention of the present invention, it is obtained by using the phosphorus-containing organic silicon compound of the fourth invention or the condensate thereof as an intermediate. A method for producing a phosphorus-containing organic silicon compound according to any one of the inventions 5 and 6 is provided.

According to a tenth aspect of the present invention, there is provided a resin composition comprising the phosphorus-containing organic silicon compound according to any of the first to sixth aspects or a condensate thereof.

Further, according to the eleventh aspect of the present invention, in the tenth aspect, there is provided a resin composition characterized in that it is a polyester resin or a polycarbonate resin composition.

Furthermore, according to the twelfth aspect of the present invention, there is provided a coating composition comprising the phosphorus-containing organic silicon compound according to any of the first to sixth aspects or a condensate thereof. Ru.

The present invention is, as described above, a phosphorus-containing organic silicon compound characterized in having, in the molecule, a phosphorus-containing group (X group) represented by the above general formula (1) bonded to a carbon atom. Etc., but as a preferred embodiment, The following are included.

(I) In the seventh or eighth invention, the reaction of the compound represented by the general formula (7) with the silicon compound having an unsaturated ester group represented by the general formula (8) or (9) is A method for producing a phosphorus-containing organic silicone compound or a condensate thereof, which is performed in the presence of a solvent.

(II) In the seventh or eighth invention, the compound represented by the general formula (7) is 3,4,5,6-dibenzo-one 1,2-oxaphosphane 1-oxide (alias: 9, 1 0) A method for producing a phosphorus-containing organic silicon compound or a condensate thereof, which is characterized in that it is a dihydric 9-oxa-1 10-phosphaphenanthrene (1 -1 0-oxide).

(III) In the tenth aspect of the invention, flame retardants, inorganic particles, organic particles, fibers, anti-drip agents, staining agents, pigments, plasticizers, cross-linking agents, UV absorbers, light stabilizers, antioxidants A resin composition comprising at least one additive selected from fungicides, antibacterial agents, fungicides or antialgal agents.

(IV) In the 12th invention, resin, staining agent, pigment, antistatic agent, crosslinking agent, anti-fog agent, viscosity modifier, dispersion aid, surfactant, nucleating agent, lubricant A coating composition characterized in that it contains at least one additive selected from UV absorbers, light stabilizers, antioxidants, fungicides, antibacterial agents, fungicides and algaecides .

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the phosphorus-containing organic silicon compound of the present invention, a method for producing the same and the same The respective resin compositions will be described in detail for each item.

1. Phosphorus-containing organosilicon compounds

The phosphorus-containing organic silicon compound of the present invention is characterized by having, in the molecule, a phosphorus-containing group (X group) represented by the following general formula (1) bonded to a silicon atom.

General formula (1):

--R ¹ 0 0

PR ³ -C 0-R 4 _ (1)

, R ² (0) m In the above general formula (1), R ¹ and R ² are the same or different, and are linear or branched alkyl groups each having 1 to 8 carbon atoms, in the ring Or an alicyclic group having 5 to 6 carbon atoms, an unsubstituted or substituted aryl group having 60 carbon atoms, or R ¹ and R ² together with a phosphorus atom It shows what forms an 8-membered cage, m is 0 or 1, and R ³ and R ⁴ each independently represent a substituted or unsubstituted divalent hydrocarbon group.

In the phosphorus-containing organic silicon compound of the present invention, in the above general formula (1), it is preferable to use a compound in which R ¹ and R ² together with the phosphorus atom form a 6 to 7-membered ring. And where an oxygen atom is present (m =

) Are counted as members of the ring. More preferably, R ¹ and R ² are the same or different and each is a linear or branched alkyl group having 1 to 4 carbon atoms, a succinic pentyl or cyclohexyl group, one or more halogens, an alkyl Or an aryl group substituted by an alkoxy or aryl group, or a compound in which R ¹ and R ² form an unsubstituted or substituted oxaphosphorin ring together with a phosphorus atom.

More preferably, R ¹ and R ² are identical and are a phenyl group or a phenyl group substituted by one or two alkyl or alkoxy groups having 1 to 4 carbon atoms each, m It is a compound which is = 0.

Most preferably, the phosphorus-containing group (X group) represented by the general formula (1) is a general formula (6 ′) containing an oxaphosphalin ring:

(Wherein, R ³ and R ⁴ each independently represent a substituted or unsubstituted 2 Ataisumi hydrocarbon group,! ^ ¹ ° Oyobi ^{1 1} may be the same or different and are each a hydrogen atom, a halogen And an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. In the general formula (6 ') Each of R ¹⁰ and R ¹¹ is preferably a hydrogen atom, and in this case, it becomes the above general formula (6) according to the sixth invention of the present invention.

Furthermore, in the phosphorus-containing organic silicon compound of the present invention, R ³ and R ⁴ in the general formula (1) each independently represent a substituted or unsubstituted divalent hydrocarbon group, preferably 1 to 1 each. It is a divalent hydrocarbon group having 8 substituted or unsubstituted carbon atoms, more preferably a substituted or unsubstituted divalent hydrocarbon group having 1 to 4 carbon atoms.

In addition, the phosphorus-containing organic silicon compound of the present invention is a compound represented by the following general formula (2):

It is characterized in that it is represented by X ¹ R ⁵ _h b S ° i ¹ O ((Λ ^4-a- _h b 1) // 92 2.

In the above general formula (2), X is a phosphorus-containing group represented by the above general formula (1), R ⁵ is an alkyl group having 1 to 30 carbon atoms, a aryl group, an aryl group, It represents the same or different organic group selected from a fluorine-substituted alkyl group or an alkoxy group, preferably each selected from an alkyl group of 1 to 8 each, a aryl group, a aralkyl group, a fluorine-substituted alkyl group or an alkoxy group Or a different organic group, more preferably a homogeneous or different organic group selected from an alkyl group having 1. to 6 carbon atoms, a aryl group, a fluorine-substituted alkyl group or an alkoxy group, and a and b indicates the numbers in the range of 0. OO la ^ l. 5 and 0 ≤ b ≤ 3. 0 respectively. The method of description of the general formula (2) is a method unique to those skilled in the art for polysiloxane, which is represented by the number of each element or group per one silicon atom. For example, R ⁵ ₃ S i O— (R ⁵ ₂ S i O)! Oo (R ⁵ XS i O). The polysiloxane represented by 1 Si R ⁵ ₃ is X ₁₀ R ⁵ _{2 16} S

¹ Ri _{^{1 1 2 θ ι 1 ι =}} ^ 1 0/1 1 2 ^ 2 ^ 6/1 1 2 ^ 1 Oi ii / iiz, and _{^{X 0. 0 9 R 5!}} . 9 3 S i O 0. 99 Can be represented.

Therefore, the phosphorus-containing organic silicon compound of the present invention represented by the general formula (2) can also be represented by the following general formula (3).

General formula (3):

R ⁵ ₃ S i 0 1 (R ⁵ ₂ S i 0) x (R ⁵ X S iO) y — S i R ⁵ ₃ (3)

Furthermore, the phosphorus-containing organic silicon compound of the present invention is represented by the following general formula (4)

XS i R ⁶ _C (OR ⁷ ) (3-c) (4) It is characterized in that the condensation product of the phosphorus-containing organic key compound represented by the general formula (4) The present invention is encompassed.

In the above general formula (4), X is a phosphorus-containing group represented by the above general formula (1), R ⁶ is an alkyl group having 1 to 30 carbon atoms, a aryl group, R 8 is the same or different organic group selected from alkyl group or fluorine-substituted alkyl group, preferably each selected from 1 to 8 alkyl group, aryl group, arylalkyl group or fluorine-substituted alkyl group; R ⁷ is an organic group, more preferably an organic group of the same or different types selected from an alkyl group, an aryl group, an aryl group, an aryl group and a fluorine-substituted alkyl group each having 1 to 6 carbon atoms; It is the same or different organic group selected from alkyl group having 1 to 30 carbon atoms, aryl group, aryl group, aralkyl group and fluorine-substituted alkyl group, preferably 1 to 8 alkyl groups and aryl group, respectively. It is the same or different organic group selected from aralkyl group or a fluorine-substituted alkyl group, more preferably 1 or more respectively. 4 alkyl group having a carbon atom, an organic group of same or different selected from Ariru group or a fluorine-substituted alkyl le group, c is Ru 0 or 1 der.

Furthermore, the phosphorus-containing organic silicon compound of the present invention is represented by the following general formula (5):

It is characterized by being represented by XSi R ⁵ _C (OS i R ⁸ ₃ ) (3-c) (5).

In the above general formula (5), X is a phosphorus-containing group represented by the above general formula (1), R ⁸ is an alkyl group having 1 to 30 carbon atoms, a aryl group, an aryl group, The same or different organic group selected from a fluorine-substituted alkyl group or an alkoxy group is shown, preferably 1 to 8 alkyl groups respectively. Or an aryl group, an aryl group, a substituted or unsubstituted alkyl group or a substituted or unsubstituted organic group selected from an alkoxy group, more preferably an alkyl group having 6 carbon atoms, an aryl group, or a substituted fluorine group. And c is 0 or 1 which is the same or different organic group selected from silyl group or alkoxy group.

2. Method for producing phosphorus-containing organic silicon compound

The process for producing a phosphorus-containing organic silicon compound according to the present invention can be carried out in particular by the following general formula (7): rR ¹⁰

P-H (7)

R ² (0) m

(Wherein, R ¹ and R ² are the same or different and each is a linear or branched alkyl group having 8 carbon atoms, an alicyclic group having 5 to 6 carbon atoms in the ring, 6 Unsubstituted or substituted aryl group having 1 to 10 carbon atoms, or one forming a 5- to 8-membered ring with a phosphorus atom, m is 0 or 1) And a compound represented by the following general formula (8) bonded to a kein atom in the molecule: o

R ⁹ -C OR ¹ - 8

(Wherein, R ⁴ represents a substituted or unsubstituted divalent hydrocarbon group, and R ⁹ represents a substituted or unsubstituted unsaturated hydrocarbon group). It has an unsaturated ester group represented by React with a key compound.

Usually, the former is used in a stoichiometric ratio with the latter unsaturated ester group or in an excess amount of either.

In addition, the compound represented by the general formula (7) can be produced by a known method, and, for example, JP-B 4 9 4 5 3 9 7, JP-A 5 0 1 7 7 9 or JP 3 It can be manufactured by the method described in JP-440-80. As a specific example, a chemical name marketed by Sanko Co., Ltd. under the trade name “SANK 01 HCA” or “SANKO — EPOCLE AN”: 3, 4, 5, 6 dibenzo-one 1, 2-oxaphosphane One 2-oxide (alias: 9, 1 0-dihydro-1 9 _ oxer 1 0-phosphaphenanthrene 1 0 0-oxyd) can be preferably used.

In the above general formula (8), as described above, R ⁹ represents a substituted or unsubstituted unsaturated hydrocarbon group, and preferably, it is preferably unsubstituted unsaturated having 1 to 8 carbon atoms. It is a hydrocarbon group, more preferably an unsubstituted unsaturated hydrocarbon group having 1 to 4 carbon atoms. .

Compound Represented by General Formula (7) and Unsaturated Ester Represented by General Formula (8) The reaction with a silicon compound having a hydroxyl group may be carried out without using a solvent, but a solvent may be used to improve the solubility.

As the solvent, alcohols such as methanol, ethanol and isopropyl alcohol, esters such as methyl acetate and ethyl acetate, saturated aliphatic carboxylic acids such as acetic acid and propionic acid, ethers such as tetrahydrofuran and dimethyl ether Amides, amines and sulfoxides are mentioned, and although not particularly limited, alcohols and saturated aliphatic carboxylic acids are preferable. The reaction temperature is not particularly limited, but is 10 to 200 ° C, preferably 11 to 150 ° C. When the reaction is carried out at these temperatures or temperatures lower than these, pressure may be applied.

In the method for producing the phosphorus-containing organic silicon compound represented by the above general formula (4) according to the fourth invention, a compound represented by the above general formula (7) and a compound represented by the following general formula (9) ):

The reaction is carried out with Y S i R (OR (39).

In the general formula (9), Y is an unsaturated ester group represented by the general formula (8), R ⁶ is an alkyl group having 1 to 30 carbon atoms, a aryl group, an aryl group or an aryl group R ⁷ represents a same or different organic group selected from a fluorine-substituted alkyl group, and R ⁷ is a same or different group selected from an alkyl group having 1 to 30 carbon atoms, a aryl group, an aryl group or a fluorine-substituted alkyl group Organic C is 0 or 1;

Furthermore, the phosphorus-containing organic silicon compound according to the present invention can be obtained by using the phosphorus-containing organic silicon compound represented by the above general formula (4) according to the fourth invention, or a condensate thereof as an intermediate. You can get it.

As the method, a phosphorus-containing organic silicon compound represented by the general formula (4) or a condensate thereof, and 1,3,5,7-octamethyltetracyclosiloxane, hexamethyldisiloxane and the like can be used. A phosphorus-containing organic silicon compound can be obtained by reacting a silicon compound (a siloxane compound) in the presence of an acidic catalyst or a reaction with a carboxylic acid and a strong acid.

3. Resin composition

As a resin that can be used for the resin composition containing the phosphorus-containing organic silicon compound of the present invention, for example, urea resin, melamine resin, polyamide resin, polyimide resin, polyester resin, alkyd resin, epoxy resin Furan resin, polyurethane resin, isocyanate resin, silicone resin, silicone resin, silicone resin, phenol resin, resorcinol resin, polycarbonate resin, polyethylene resin, polypropylene resin, polybutadiene resin, polybutadiene resin, polyisoprene resin, polycarbonate resin, polystyrene resin, These resins include but are not limited to, but are not limited to, urea resins, polyvinyl alcohol resins, acrylic resins, butyl acetate resins, polychlorinated burles resins, or composite resins of these resins and other polymers or low molecular compounds. Absent. It is preferably a polyester resin or a polycarbonate resin, more preferably a polycarbonate resin. In the resin composition containing the phosphorus-containing organic silicon compound of the present invention, if necessary, a flame retardant substance such as aluminum hydroxide, silicon compound, antimony compound, organic halogen compound, phosphorus compound, etc. ), Calcium carbonate, barium sulfate, calcium fluoride, talc, kaolin, calcium oxide, alumina, titanium dioxide, zirconium dioxide, inorganic particles such as iron oxide, alumina / silica composite oxide, crosslinked polystyrene, crosslinked polymethacryl Organic particles such as acid ester and cross-linked polyacrylate, carbon fiber, fiber such as glass fiber, anti-drip agent, inorganic and / or organic stain, pigment, plasticizer, cross-linking agent, UV absorber, light stabilizer Antioxidants, antifungal agents, antibacterial agents, antifungal agents, antialgal agents, etc. may be contained.

The resin composition containing the phosphorus-containing organic silicon compound of the present invention has flame resistance, flame retardancy, antibacterial properties (in particular, antibacterial durability), is also considered in terms of safety, and in particular surface performance and resin performance. Can be demonstrated as a molded product such as a fiber or a film, a coating agent, or another treating agent. 4. Composition for coating

Also, the phosphorus-containing organic silicon compound of the present invention can be suitably used as a main component of a coating agent or coating composition for various substrates. In particular, it is more effective than conventional coating agents on metal substrates that are easily deformed, such as steel plates and copper plates, and is useful. When it is used as a coating composition containing the above-mentioned phosphorus-containing organic silicon compound, it may be applied as it is, but it is preferable to dilute it with a solvent because it is easy to apply uniformly and uniformly. Also, if necessary, it is usually used in a coating composition, if desired. Resins, inorganic and organic stains, pigments, antistatic agents, crosslinkers, antifogging agents, viscosity modifiers, dispersing aids, surfactants, nucleating agents, lubricants, UV absorbers, light stabilizers, oxidation Antifungal agents, fungicides, antibacterial agents, fungicides, algaecides, etc. may be contained. Example and comparative example

Next, the present invention will be described in more detail based on examples and comparative examples, but the present invention is not limited to these examples.

[Example 1]

3, 5-methacryloxypropylmethyldimethyxsilane 2 5.9 g (0. ll monol), 3, 4 in a 50 Om 1 4 loft flask fitted with a stirrer, nitrogen gas inlet, condenser and thermometer. 4, 5, 6-Dibenzo 1 1, 2-Oxaphos Fan 1 2-Oxide (alias: 9, 1 0-Dich Draw 9 1 Oxa 1 1 0-Phosphaphenanthrene 1 1 0 0-Oxide) 24 Add 1 g (0.12 mol), 5.0 g of methanol, add nitrogen gas, heat to 150 ° C while removing methanol, react for 12 hours with stirring, and react Obtained 5 g of product. The product thus obtained was examined for its structure by GPC, IR absorption spectrum, iH-NMR and mass spectrum, and the product contains a phosphorus-containing compound represented by the following chemical formula It was confirmed to be an organic silicon compound (A).

[Example 2]

Using the same apparatus as in Example 1, 3-metatallyloxyprovirtrime xylosilane 1 64. 1 g (0. 66 mono-), 3, 4, 5, 6-dibenzo 1 1, 2 -oxa phosphan 1 — Put 5 5 g (0. 6 3 mol) of Oxidized 1 3, flow nitrogen gas, heat to 150 0 C, stir for 14 hours to react,

2 8 2. Obtained O g of product. The product thus obtained was examined for its structure by GPC, IR absorption spectrum, ¹ H-NMR and mass spectrum. The product is a phosphorus-containing organic compound represented by the following chemical formula: It was confirmed to be a carbon compound (B). (Molecular weight 464. 5, viscosity about

1 7, 000 mm ² / s Refractive index 1. 5 6 7). In addition, 3, 4, 5, 6-dibenzo-1,2-oxaphosphane and 2-oxide are dissolved (melting point: 1 10 to 10)

Stirring (30 r p m) was carried out slowly until the temperature reached 120 ° C. -

[Example 3]

Using the same apparatus as in Example 1, the compound 149.2 g (0.33 mol) obtained in Example 1 was obtained. 1, 1, 3, 3, 5, 5, 7, 7-octamethyl tete 3.28 g (0 monole) of hexachlorosiloxane, 8.00 g (0.11 monole) of hexamethinodisiloxane, toluene 100 g, sulfuric acid 5 g, water 4. 8 g, room temperature After stirring for 10 hours, the reaction mixture was neutralized with sodium bicarbonate, washed with water and heated under reduced pressure to distill off the low volatile matter, and the product obtained by distilling off the volatile matter was subjected to GPC, IR absorption spectrum, ¹ H-NMR. And, when the structure was examined by mass spectrometry, it was confirmed that the product is a phosphorus-containing organic silicon compound (C) represented by the following chemical formula.

[Example 4]

Using the same apparatus as in Example 1, 3-methacryloxyprovir (trimethy noloxyl) silane 19.6 6 g (0.4 7 mol), 3, 4, 5, 6-dibenzo 1 Add 1, 2- oxaphos phan-1-1-1 10-1.4 g, 50 g of propionic acid, heat and stir at 150 ° C for 17 hours, and then depressurize. The solvent was removed to give 2 5 5. O g of product. The product thus obtained was examined for its structure by GPC, IR absorption spectrum, —NMR and mass spectrum, and the product was determined to be a phosphorus-containing organic silicon compound represented by the following chemical formula ( D) was confirmed.

[Example 5]

The same apparatus as in Example 1 was used and the compound 9 obtained in Example 2 was obtained. 5.6 g (0.20 mono), hexamethyldisiloxane 6 0. O g (0. 30, 70 mol) 4.4 g (0.04 mol) of acetic acid and 6.O g of sulfuric acid are reacted, 100 g of toluene is added, neutralized with sodium bicarbonate, washed with brine, and heated under reduced pressure. The solvent and the low volatiles were removed to give 82 g of product. The structure of the product thus obtained was examined by GPC, IR absorption spectrum, iH-NMR and mass spectrum, and the product was found to have the same ring as the compound obtained in Example 4. It was confirmed that the contained organic silicon compound (D) (refractive index 1. 5 6 7).

[Comparative example 1]

Using the same apparatus as in Example 1, vinylmethyldimethoxysilane 19.0 g (0.14 44 mol), 3, 4, 5, 6-dibenzo-l 1, 2-oxaphos-phan 1-oxide 3 1. 0 g (0.1 4 44 mol), methanol 25. 0 g, The mixture was flushed with nitrogen gas, heated to 150 ° C. while removing methanol, and stirred for 12 hours. However, no reaction occurred, and only the raw material was recovered.

Comparative Example 2

The conditions were the same as in Comparative Example 1 except that 10 g of a 5% methanol solution of sodium methoxide was added, but no reaction occurred, and only the raw material was recovered.

[Comparative example 3]

Under the same conditions as in Example 2 except that 6 g of a 5% methanol solution of sodium methoxide was added, the same compound as the compound obtained in Example 2 was obtained. The yield was low.

[Examples 6 to 26, Comparative Examples 4 to 5] (Preparation and Evaluation of Resin Composition) Resins, phosphorus-containing organic silicon compounds obtained in Examples or Comparative Examples, and formulations according to the formulations shown in Tables 1 to 3 below. Arbitrary components were mixed, and pelletized by extruding at a cylinder temperature of 250 ° C. using a 40 mm diameter single-axis extruder [manufactured by Isuzu Kogyo Co., Ltd.].

After drying each of the obtained pellets at 120 ° C. for 6 hours, a cylinder temperature of 270 ° C. and an injection molding machine (manufactured by Japan Steel Works, Ltd., trade name “J-50 EP”) are used. A molded body (test piece for evaluation or measurement) is produced at a mold temperature of 80 ° C, and the flame retardant performance (after initial storage) and the appearance state of the molded body are evaluated, and the bending elastic modulus is also measured. Izod impact strength and heat distortion temperature were measured. The above results are shown together in Tables 1 to 3 below. Here, evaluation and measurement methods of the molded body (resin composition) are as follows.

[Flame Retardant Performance (Initial)]

Tests were conducted using specimens with a thickness of 1/16 inch (5 pieces per resin composition) manufactured in accordance with the UL 94 standard, and the flame retardant performance was evaluated based on the following criteria. did.

(V-0): The flame burning time after removing the additive flame is within 10 seconds, and the total flame burning time of 10 times of flame contact with 5 pieces of sample is within 50 seconds. Also, for all samples, do not drop the fine particle flame that ignites absorbent cotton.

(V-1): The flame burning time after removing the additive flame is within 30 seconds, and the total flame burning time of 10 times of flame contact with 5 pieces of samples is within 250 seconds Yes, and all samples do not fall on the fine particle flame that ignites absorbent cotton.

(V-2): The flame burning time after removing the additive flame is within 30 seconds, and the total flame burning time of 10 times of flame contact with 5 pieces of samples is within 250 seconds Yes, and these samples fall fine flames which ignite absorbent cotton.

[Flame retardant performance (after storage)]

A test piece (5 pieces per 1 resin composition) with a thickness of 1/16 inches, which was manufactured in accordance with the U L 94 standard, has a temperature of 26. C, after standing for 6 months in a constant temperature and humidity chamber with a relative humidity of 65%, the same test as described above was performed to evaluate the flame retardant performance

[Appearance]

The molded product is visually observed, and if it is very good, "◎", it is good “X” is given for the case where it is not good, and “X” when it is not good.

[Flexural modulus]

The flexural modulus of the test piece prepared in accordance with ASTM standard D_790 was measured.

[Izos impact strength]

A 18-inch thick notched impact test specimen is prepared in accordance with H.8-3 1 ^ Standard 13- 2 5 6, and in accordance with ASTM D- 2 56, Izod impact strength (2 3 ° C was measured.

[Heat deformation temperature]

The deflection temperature under load under a load of 1802 kPa was measured using a test piece manufactured in accordance with ASTM standard D- 648.

Example 6 7 8 9 10 11 12 13 Types of Resin PC PC PC PC PC PC PC PC Phosphorus-containing organic silicon

Compound (mass%) * 1

• A (Example "!) 2-2

■ B (Example 2) 2 2

• C (Example 3) 2

■ D (Examples 4 and 5) 2 10 2 Other additives (% of quality improvement)

商下 J | J 0.5

One

'Tarek 7.5 15 15 Performance evaluation

Flame retardant performance (grade)

, Initial V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0

• After storage V-0 V-0 V-0 V-0 V-0 V-0 V-0 Appearance Condition ◎ ◎ ◎ ◎ ◎ ◎ 弾性 Flexural modulus (10 ³ x Kg m ² ) 22 22 24 23 22 50 50 51 Impact strength (Kg'cm Z cm) 82 82 80 81 84 45 45 Heat distortion temperature (° c) 136 136 132 134 136 138 140 140

* 1 · · · Composition total amount standard

* 1: Total composition standard

≠ 2

* 1: Total composition standard

The trade names of the resins or the components shown in Tables 1 to 3 are as follows.

■ Polycarbonate (PC) Resin: Sumitomo Caliber 'Caliver 300'-Acrylonitrile-Butadiene-Styrene (AB S) Resin: Mitsui Toatsu Chemical 'Santak UT-6 1' or Daicel Chemical Industries "Sevien V 1 6 S 0"

• Polybutylene terephthalate (P B T) resin: "Toughpet P B T" manufactured by Toyobo

-Atelier rate-Styrene-Acrylonitrile (A SA) Resin: "Dialac A" made by Mitsubishi Rayon

Styrene first water tri-roll (S AN) resin: "Den force A S" made by Denki Kagaku Kogyo

'Polyethylene terephthalate (P E T) Resin: Mitsubishi Rayon's "D

• Polystyrene (PS) resin: “Idemitsu polystyrene” made by Idemitsu Petrochemical-Anti-drip agent: “Polyflon F 20 1 LJ made by Daikin Chemical Industries, Ltd.

'Sir corn powder: Dow Corning's "DC 4 _ 7 0 5 1"

As is clear from the performance evaluation results shown in Tables 1 to 3, it is apparent that the molded product comprising the resin composition containing the phosphorus-containing organic silicon compound of the present invention has a flame retardant performance (after initial Z storage), an appearance The performance in terms of state, flexural modulus, Izod impact strength, and heat distortion temperature was good.

[Example 2 7 and Comparative Example 6] (Preparation and evaluation of composition for coating) The phosphorus-containing organic silicon compound obtained in Example 2 as Example 2 7 A coating composition was obtained by uniformly mixing 0 parts by mass, 20 parts by mass of tetraethoxysilane, and 5 parts by mass of isopropyl alcohol 4.

The coating composition was applied to a 3 × 10 cm copper plate and left in a room at 25 ° C. for 24 hours to obtain a cured film. This was placed in a glass bottle containing 30 g of a 0.5% aqueous solution of hydrochloric acid and left for 3 hours. As a comparison (blank), a copper plate which has not been coated (coated) was also stood at the same time in the glass bottle for the same time.

The copper plate treated with the coating composition of the present invention did not change at all in the portion on the liquid surface, and maintained the initial color although the portion below the liquid surface was somewhat deteriorated in gloss. On the other hand, in the copper plate which has not been coated (coated), the portion on the liquid surface turns dark red, and the portion under the liquid surface loses its luster and turns brownish. Comparative example 6 shows 3.0 mass of methyltrimethoxysilane. A coating composition was obtained by uniformly mixing 20 parts by mass of tetraethoxysilane and 5 parts by mass of isopropyl alcohol 4.

The same evaluation as in Example 7 was carried out. As with the copper plate not coated (coated), the portion on the liquid surface turned dark red and the portion below the liquid surface turned dull and turned brown. Industrial applicability

As described above, the present invention provides a novel phosphorus-containing organic silicon compound, a method for producing the same, and a resin composition or a coating composition containing the same. This phosphorus-containing organic silicon compound has flame resistance, flame retardancy, antibacterial properties (especially antibacterial durability), is also considered for safety, and is particularly suitable for use as a resin by applying it to a resin. Since the performance and resin performance are modified, the effects can be exhibited as molded articles such as fibers and films, coating agents, and other treating agents. In particular, they have extremely excellent properties as flame retardants of various resins, and can exhibit 5 to 20 times the flame retardancy performance as compared to the case where the conventionally known phosphorus-based flame retardants are used in the same mass. . Therefore, since the amount of addition to the resin can be significantly reduced, it is possible to substantially prevent problems such as a decrease in the mechanical strength of the resin composition (molded body) and thermal deformation due to the addition of the flame retardant. .

Claims

The scope of the claims

1. A phosphorus-containing organic silicon compound characterized by having a phosphorus-containing group (X group) represented by the following general formula (1) bonded to a carbon atom in a molecule. — General formula (1):

—-R ¹ 0 0

P— R ³ — C 0-R ⁴ (1)

R ² (0) m

(Wherein, R ¹ and R ² are the same or different and each is a linear or branched alkyl group having 1 to 8 carbon atoms, and an alicyclic group having 5 to 6 carbon atoms in the ring , An unsubstituted or substituted aryl group having 6 to 10 carbon atoms, or one forming a 5- to 8-membered ring with a phosphorus atom, m is 0 or 1; R ³ and R ⁴ each independently represent a substituted or unsubstituted divalent hydrocarbon group.)

2 General formula (2

X, R ⁵ S i 〇 (4 1 b) (2

[Wherein, X is a general formula (1 0 o

PR ^3- C 0 — IT (1)

^L R ² (0) m

(Wherein, R ¹ and R ² are the same or different and each represents a linear or branched alkyl group having 1 to 8 carbon atoms, and an alicyclic group having 5 to 6 carbon atoms in the ring , An unsubstituted or substituted aryl group having 6 to 10 carbon atoms, or one forming a 5- to 8-membered ring with a phosphorus atom, m is 0 or 1 And R ³ and R ⁴ each independently represent a substituted or unsubstituted divalent hydrocarbon group.

R ⁵ is a phosphorus-containing group represented by the formula: R ⁵ represents a homogeneous or different organic group selected from an alkyl group having 1 to 30 carbon atoms, a aryl group, an aryl group, a fluorine-substituted alkyl group or an alkoxy group , A and b indicate the numbers in the range of 0. 0 0 1 ≤ a ≤ 1.5, 0 ≤ b ≤ 3. 0, respectively. ]

A phosphorus-containing organic silicon compound characterized by being represented by

3. The phosphorus-containing organic silicon compound according to claim 2, wherein the general formula (2) is represented by the following general formula (3).

General formula (3):

R ⁵ ₃ S iO— (R ⁵ ₂ S i)) X (R ⁵ X S i O) y S i R ⁵ ₃ (3) (wherein, R ⁵ and X represent the same as above,. X Is 0 or 1 or more Is an integer, y is an integer greater than or equal to 1,

4 General formula (4)

XS i R ⁶ _r (OR (3 4

[Wherein, X is a general formula (1): rR ¹ 0 0

PR ³ -C 0-R 4_ (1)

R ² (0) m

(Wherein, R ¹ and R ² are the same or different and each is a linear or branched alkyl group having 8 carbon atoms, an alicyclic group having 5 to 6 carbon atoms in the ring, 6 And n represents an unsubstituted or substituted aryl group having 1 to 10 carbon atoms, or one forming a 5- to 8-membered ring with a phosphorus atom, m is 0 or 1, R ³ And R ⁴ each independently represent a substituted or unsubstituted divalent hydrocarbon group.)

R ⁶ represents a same or different organic group selected from an alkyl group having 1 to 30 carbon atoms, a aryl group, an aryl group and a fluorine-substituted alkyl group, ⁷ is the same or different organic group selected from an alkyl group having 1 to 30 carbon atoms, an aryl group, an aryl group and a fluorine-substituted alkyl group, and c is 0 or 1. ] And a phosphorus-containing organic silicon compound represented by the following general formula (5)

XS i R ⁵ _C (OS i R 3) (3-c) 5

[Wherein, x is a general formula (1): r -R ¹ 0 0

PR ³ -C 0 -R ^A R ² (0) m

(Wherein, 1 ¹ Oyopi 1 ² may be the same or different, each 1-8 straight-chain or branched alkyl group having carbon atoms, alicyclic having 5 to 6 carbon atoms in the ring And m represents 0 or 1, and represents a group having a formula group, an unsubstituted or substituted aryl group having 60 carbon atoms, or one forming a 5- to 8-membered ring together with a phosphorus atom. R ³ and R ⁴ each independently represent a substituted or unsubstituted divalent hydrocarbon group.)

And R ⁵ represents a same or different organic group selected from an alkyl group having 1 to 30 carbon atoms, a aryl group, an aryl group, a fluorine-substituted alkyl group or an alkoxy group. R ⁸ represents an alkyl group having 3 carbon atoms, a aryl group, an arylalkyl group, a fluorine-substituted alkyl group or an aryl group C is an organic group of the same or different type selected from coxy groups; c is 0 or ]

A phosphorus-containing organic silicon compound _{c characterized by}

6. The ring-containing group (X group) is represented by the following general formula (6):

(Wherein, R ³ and R ⁴ each independently represent a substituted or unsubstituted divalent hydrocarbon group).

It is a compound represented by these, The phosphorus containing organic silicon compound in any one of the Claims 1-5, or its condensate.

7. General formula (7) below: fR ¹ 0

P-H (7)

^L R ² (0) m

(Wherein,! ¾ ¹ Oyobi ^2, the or different, linear or branched alkyl group, an alicyclic group having 5 to 6 carbon atoms in the ring having 8 carbon atoms in each , An unsubstituted substituted having 6 to 10 carbon atoms Or a substituted aryl group or one forming a 5- to 8-membered ring with a phosphorus atom, and m is 0 or 1. )

And a compound represented by the following general formula (8) bonded to a silicon atom in the molecule:

0

R ⁹ -C 0 — IT 8

(Wherein, R ⁴ represents a substituted or unsubstituted divalent hydrocarbon group, and R ⁹ represents a substituted or unsubstituted unsaturated hydrocarbon group).

The phosphorus-containing organic silicon compound or the condensate thereof according to any one of claims 1 to 6, which is obtained by reacting with a silicon compound having an unsaturated ester group represented by Manufacturing method.

8 General formula (7) 厂 ... -R ¹ 0

PH (7) and R ² (0) m

(Wherein, R ¹ and R ² are the same or different and each is a linear or branched alkyl group having 8 carbon atoms, an alicyclic group having 5 to 6 carbon atoms in the ring, 6 Form a 5- to 8-membered ring together with an unsubstituted or substituted aryl group having 1 to 10 carbon atoms, or a ring atom , M is 0 or 1. )

And a compound represented by the following general formula (9):

YS i R ⁶ _C (OR ⁷ ) (3-c) 9

[Wherein, Y is a general formula (8)

0

R ⁹ -C 0- R ⁴ - 8

R ⁶ represents the same or different organic group selected from an alkyl group having 1 to 30 carbon atoms, a aryl group, an aryl group and a fluorine-substituted alkyl group, and R ⁷ represents an unsaturated ester group represented by And the same or different organic group selected from an alkyl group having 1 to 30 carbon atoms, a aryl group, an aryl group or a fluorine-substituted alkyl group, and c is 0 or 1. ]

The method for producing a phosphorus-containing organic silicon compound or a condensate thereof according to claim 4, which is obtained by reacting with a silicon compound represented by

9. The phosphorus-containing organic silicon compound according to claim 4 or a condensate thereof, which is obtained by using it as an intermediate. The manufacturing method of the phosphorus containing organic silicon compound in any one of 5 and 6.

A resin composition comprising the phosphorus-containing organic silicon compound according to any one of claims 1 to 6 or a condensate thereof.

11. The resin composition according to claim 10, which is a polyester resin or a polycarbonate resin composition.

A coating composition comprising the phosphorus-containing organic silicon compound according to any one of claims 1 to 6 or a condensate thereof.